Addition of N,N-dichloro-N-acyl compounds to dienes

ABSTRACT

N,N-Dichloro-N-acyl compounds, such as N,N-dichlorocarbamates, sulfonamides and amidosulfonamides selectively react with conjugated dienes to yield the corresponding 1,4-monoadducts, i.e. N-chloro-N-chlorocrotyl compounds. The N-chloro group of these monoadducts can be selectively reduced by aqueous sodium sulfite. Both the original and the reduced adducts are novel compositions useful as biologically active compounds and vulcanizing agents.

Daniher et al.

ADDITION OF N,N-DICHLORO-N-ACYL COMPOUNDS TO DIENES Inventors: Francis A. Daniher, Westfield;

Alexis A. Oswald, Mountainside, both of NJ.

Exxon Research & Engineering Company, Linden, NJ.

Filed: Dec. 6, 1967 Appl. No.: 688,308

Assignee:

References Cited UNITED STATES PATENTS 6/1934 Ulrich et al 260/482 X [451 May 20, 1975 2,395,750 2/1946 Muskat et al. 260/482 X 3,477,933 11/1969 Stamm et al. 260/482 c FOREIGN PATENTS OR APPLICATIONS 1,203,534 6/1962 Germany 260/482 c Primary ExaminerLorraine A. Weinberger Assistant ExaminerPaul J. Killos Attorney, Agent, or FirmJ. N. Blauvelt; J. P. Corcoran 57 ABSTRACT N,N-Dichloro-N-acyl compounds, such as N,N- dichlorocarbamates, sulfonamides and amidosulfonamides selectively react with conjugated dienes to yield the corresponding 1,4-monoadducts, i.e. N-chloro-N- chlorocrotyl compounds. The N-chloro group of these monoadducts can be selectively reduced by aqueous sodium sulfite. Both the original and the reduced adducts are novel compositions useful as biologically active compounds and vulcanizing agents.

27 Claims, N0 Drawings ADDITION OF N,N-DlCI-ILORO-N-ACYL acts in the same manner with two moles of a conjugated COMPOUNDS TO DIENES diene as per the following equation; e.g.,

THE INVENTION 7 O The present invention relates to a novel, selective diene addition process resulting in new, useful carba- R 0CNC1 2 CH =CH CH mates heretofore unavailable in the art. More particularly, this invention describes the selective addition of N,N'-dichlor0-acyl compounds, such as N,N-

dichlorocarbamates, N,N-dichlorosulfonamides, N,N- 10 dichloroamidosulfonamides to conjugated dienes yield- 0 ing N-chlorocrotyl acyl compounds. H

N-Acyl compounds such as carbamates and sulfona- I 2 F 'Z CH=CHCH2Cl mides are a known useful class of compounds. For example, carbamates or urethanes are a widely known Cl 2 type of compounds. Some of them are extremely useful in the pesticide, pharmaceutical and polymer industry. The resulting N-chloro-N-chlorocrotyl carbamates The importance of selected members of N-acyl comcould be reduced by sodium sulfite to yield a surprispounds has stimulated interest in new types of carbaingly high yield of the corresponding N-chlorocrotyl mates, sulfonamides and amidosulfonamides and novel carbamate, eig. methods of preparing such compounds.

The addition of N-chloro dialkylamines to a conjugated diene, 1,3-butadiene was reported to occur in O acidic medium to yield up to 60% of the corresponding 1,4-adducts (R. s. Neale and R. L. Hinman, J. Am. RPCNCH CH=CHCH Cl Na SO +H 9 Chem. SOC. 85, 2666 (1963)).

The addition of N,N-dichlorocarbamates to a variety of O monoolefins has been recently reported to yield the corresponding anti-Markovnikov adducts in yields gen- RPCNCH CH=CHCH C1 NaHSO +Na Cl erally ranging from 25-65%. (One high yield exception 1 2 2 LL was the addition to styrene where an 80% yield was ob- H tained):

0 o o NaI-ISO 12906101 CH2 CHR BpCNCH CH R RPCNCHQCHQH' I I I 1 C1 C1 H Cl ln the present invention, it has been found surpris- The reduction of the N-chloro group of carbamates ingly that the addition of N,N-dichlorocarbamates to With Sodium hydrogen sulfite is a known process. It was 1,3-butadiene in neutral media gives a quantitative found that for the reduction of our chlorocrotyl caryield of the corresponding monoadducts in a spontanebamate adducts the use Of dium ulfite is much prefous reaction. erable.

o I O I! ll ll R C CH: 1 OCNCH CH CH=CH R oCNCl CH ca CH CH -9- o 1:1CH cncn c R I 2 2 2 C1 C1 C1 Characteristic of the addition to l,3-butadiene and The addition of other N,N-dichloro acyl compounds, other conjugated dienes is the fact that the predomisuch as N,N-dichloro sulfonamides and N,N-dichl0ro nant mode of addition to the diene is l,4-addition withdialkylamidosulfonamides to conjugated dienes was out formation of diaddition products to the diene. also found to occur with a surprising ease and selectivity as shown for butadiene additions by the following Similarly, one mole of a difunctional carbamate rereaction equations;

These N-chloro-N-chlorocrotyl adducts can be again advantageously reduced by sodium sulfite to the corresponding N-chlorocrotyl compounds:

The above addition and reduction processes lead to novel types of acyl compounds as shown by the following reaction scheme:

wherein Ac is an acyl group such as carboalkoxy, ROCO, hydrocarbyl sulfonyl R"SO dialkylamidosulfonyl, (R"') NSO R to R7 are hydrogen, chlorine, fluorine, an alkyl group having from 1 to 30 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, heptyl, decyl, dodecyl, tridecyl, hexadecyl, eicosyl, etc.; substituted alkyl where the substituents are selected from the group consisting of halo, nitro,

wherein R2 to R1. are the same as previously defined. R, is an alkyl or substituted alkyl group having from 1 to carbon atoms, such as a simple alkyl group exemplified by methyl, ethyl, isopropyl, tertiary butyl, dode- 5 cyl, hexadecyl, etc. and a substituted alkyl group where the substituents are selected from the group consisting of halo, nitro, sulfone, carboxylic ester having 2 to 6 carbon atoms, etc.

Bis-N,N-dichloro carbamates can be also added to I0 conjugated dienes to yield the following novel compositions:

wherein R to R are the same as previously described,

R is a bivalent alkylene or substituted alkylene radical having from 1 to 12 carbon atoms such as ethylene, hexamethylene, xylylene, etc.

Furthermore, the addition of N,N-dichloro sulfona- "mides to conjugated dienes specifically produces novel monooadducts which can be reduced with sodium sulfite as shown in the following:

sulfone, CO R; aryl having from 6 to 10 carbon atoms such as phenyl; substituted aryl such as aralkyl, including benzyl, beta-phenethyl, and other substituted forms of aryl wherein the substituents are selected from the group consisting of halo, nitro, carboxyl, CO R, etc., phenyl and substituted phenyl having 6 to 10 carbon atoms such as nitrophenyl, chlorophenyl, xylyl, etc.

More particularly, the addition of N,N-dichloro carbamates, i.e. dichlorourethanes to conjugated dienes and the reduction of the resulting monoadducts yields the following types of novel compositions:

8 M 3 C: C C C R SO NCl R"SO2N c c=' oc c1 Na2303 I I I I C111 R R R R R I2 IL- 1 I6 -R"SO2NC-C=C-CCl I I I H R3 R wherein R to R are the same as previously defined R" is a hydrocarbyl or a substituted hydrocarbyl having l to 30 carbon atoms such as methyl, hexadecyl, tri- The invention specifically includes the compoundsderived by the additionof N,N-dichloro N',N-dialkyl sulfamides to conjugated dienes and by the subsequent reduction of the adducts:

Cl R R i T T "6" -c=c-c-c1 NSO 1 I c I H R R wherein R to R are the same as previously defined, R' is an alkyl group having from 1 to 20 carbon atoms such as methyl, isopropyl, hexadecyl.

The novel reactions described in the present invention produce the following types of novel compositions:

R R4 R R II I I I I X R R Carbamates R2 RLLIR5 R6 1 I I I R"s0 N -C -C =C- C- Cl I I I X R3 R7 sulfonamides ewe ROCN-C -C=C-C-C1 l I I X R R Bis-Carbamates R R4 R R I I I I X R3 R7 Sulfamides wherein R to R R R, R", R' are as previously defined and X is chlorine and hydrogen. In the pesticide and medicinal compositions of the present invention, X is chlorine and hyrogen while in the vulcanization additives X is always chlorine.

'In a preferred embodiment of this invention, N,N-

dichloro acyl compounds can be reacted with 1,3-

butadiene at low temperatures, e.g. between l0 and +C. Other conjugated dienes may be used. The pre- 5 ferred dienes include isoprene, 1,3-butadiene, chloro-' prene; l-phenyl butadiene, 1,4-diphenylbutadiene; 2,3- dimethylbutadiene; piperylene; 2,3-dichloro-l,3- butadiene; 2-ethyl-l,3-butadiene; 1,3-hexadiene; 2,4-

hexadiene; 2-methyl-l ,3-pentadiene; 4-methyl-l ,3- pentadiene. Other, less preferred, dienes that are suitable for use in this invention include 1,3-

cyclohexadiene; 1-chloro,l ,3-butadiene; cyanoprene; fluoroprene, l ,3-cyclooctadiene; 2,5-dimethyl-2,4- hexadiene; cyclopentadiene, etc. The foregoing enumeration of dienes is merely intended to be a representative, and not exhaustive, listing of dienes suitable for application within the scope of this invention.

As N,N-dichloro acyl compounds N,N-dichloro carbamates may be used. Examples of suitable N,N- dichlorocarbamates are the following: N,N- dichloroethyl carbamate, N,N-dichlorohexadecyl carbamate, N,N-dichloro-i-propyl carbamate, N,N- dichlorocyclohexyl carbamate, N,N-dichloro-2- chloroethyl carbamate, N,N-dichloro-Z-nitroethyl carbamate, N,N-dichlorotrifluoroethyl carbamate, N,N- dichloromethylsulfonylethyl carbamate, N,N- dichlorotrichloromethyl carbamate, N,N-dichlorocarbomethyloxyethyl carbamate, N,N-dichlorobenzyl carbamate. Any alkyl or substituted alkyl ester of'N,N- dichlorocarbamic acid can be used as a starting material as long as the alkyl portion does not contain any substituent which would react with the N,N- dichlorocarbamate group. For example, vinyl-, mercapto-, or aminosubstituted dichloro carbamates would not be suitable.

Suitable bis-N,N-dichloro carbamate reactants include ethylene bis-N,N-dichloro carbamate, hexamethylene N,N-dichloro carbamate, p-xylylene N,N- dichloro carbamate, etc.

Another class of N,N-dichloro acyl compound reactants consists of N,N-dichloro sulfonamides. Suitable N,N-dichloro sulfonamides are exemplified by the following: N,N-dichl0ro methanesulfonamide, N,N- dichloro trichloromethanesulfonamide, N,N-dichloro chloroethanesulfonamide, N,N-dichloro dodecanesulfonamide, N,N-dichloro benzenesulfonamide, N,N- dichloro 4-chlorobenzenesulfonamide, N,N-dichloro 2,4,5-trichlorobenzene sulfonamide, N,N-dichloro 4- 5O toluenesulfonamide, N,N-dichloro 2- naphthalenesulfonamide.

A third class of N,N-dichloro acyl compounds which can be added to conjugated dienes according to the present invention is represented by N,N-dichloro Suitable N,N-dichloro dialkyl amidosulfonamides.

amidosulfonamides are N,N-dichloro dimethylamidosulfonamide, N,N-dichloro diisopropylamidosulfonamide, N,N-dichloro dihex adecylamidosulfonamide.

The general reaction conditions that may be utilized in the addition process of this invention comprise temperatures ranging from about 80 to about 100C, preferably from about 20 to about +30C. The reaction time is dependent upon the rate of addition and it may vary from spontaneous reaction to about 8 hours,

depending upon the choice of reactants and the reaction conditions but may take as long as about 24 hours,

assuming proper mixing of reactants. Ordinarily, however, the reaction should take no longer than about 1 hour.

Pressures ranging from 1 to 10 atmospheres can be used. Preferably, however, the reaction is conducted at atmospheric pressure.

Preferably, the ratio of reactants is equimolar; however, excess diene can be used. In general, the ratio of reactants can vary from 1:1 to about 5:1 moles of diene per mole of N,N-dichloro acyl compound. While an excess of N,N-dichloro compound could be used, this is not at all preferred since any excess of this reactant constitutes a waste thereof. From the previous equations, it is manifest that, with a difunctional carbamate, a minimum of two moles of the diene reactant is required.

Various solvents useful in the foregoing process,

preferably inert solvents, include such solvents as paraffinic and aromatic hydrocarbons and their halo derivatives, such as, for example, dichloromethane, carbon tetrachloride, benzene, xylene, chlorobenzene, chloroform, methylene chloride, pentane, iso-octane, decalin, etc. Preferred solvents include the aliphatic and alicyclic hydrocarbons and their chlorinated derivatives such as cyclohexane, etc. In general, any suitable solvent that is either inert or substantially inert under the reaction conditions such that it does not react with the reactants to any substantial extent is useful within the purview of this invention.

In the reduction process the temperature is from 20 to 100C., preferably from 0 to 50C. The sodium sulfite reducing agent is preferably used in the form of a concentrated aqueous solution. An inert organic solvent such as a chlorinated hydrocarbon is used as a solvent for the N-chloro-N-(4-chlorocrotyl-l compound to be reduced. The reduction is effected while the reaction mixture is vigorously stirred. The reduction usually requires several hours. The completion of the reaction is usually established using a potassium iodide test for the disappearance of the N-chloro group.

As previously noted, the N-chlorocrotyl compounds of this invention are useful as pesticides. One aspect of such pesticidalapplication is as a herbicide, preferably as post-emergent, or as a fungicide. When used as a fungicide or herbicide, the compositions of this invention may be used to control plant growth or fungi thereon either applying to foliage or plant growth media, a growthor fungi-controlling dosage of the present acyl compound or of concentrated compositions prepared from many of the aforesaid compounds (as an active ingredient) in intimate admixture with at least one'material of the group consisting of finely-divided inert solids, granular solids, surface active dispersing agents, beeswax, paraffin waxes, water, organic solvents, nitrogen fertilizers, potassium fertilizers, meta phosphates, etc. Particularly contemplated as desirable concentrate compositions are those which comprise the aforesaid novel chlorocrotyl compounds of this invention as active ingredients in an intimate admixture with at least one material of the group consisting of finely-divided solids, inert granular solids, and surface active dispersing agents.

The expression surface active dispersing agent as herein employed is intended to include all agents which are capable of acting at the interfacial surface between the aforesaid carbamate derivative or composition and water or organic solvents as the dispersion dispersant media, facilitating thereby the dispersion of the toxicant in water or organic solvents to form aqueous and emulsified concentrate. The term is inclusive of solid emulsifying agents such as finely divided bentonite, pyrophyllite, fullers earth, attapulgite, silica, other clays and mineral carriers, as well as liquid and solid ionic and non-ionic wetting and dispersing agents, alkaline metal caseinates, alkyl aryl sulfonates, sulfonated oils, complex organic ester derivatives, condensation products of alkene alkaline oxides and organic acids, mahogany soaps, etc.

Other suitable surface active dispersing agents may be found in Detergents and Emulsifiers, Up to Date", written and published by John W. McCutcheon, Inc., New York, 1962.

The term finely divided inert solids as herein employed refers to material whose primary function is not as dispersant of the present N-chlorocrotyl derivatives in water or organic solvents, but as carrier for dust compositions. Illustrative of such carriers are materials such as chalk, talc, gypsum, etc.

The term inert granular solids refers to mineral or other inert carriers which are suitable for dry application and which include corn cobs, sand, and other materials which differ primarily in particle size from the finely divided inert solids.

According to the present invention, any of the appropriate crotyl derivatives disclosed herein may be compounded with any of the finely divided solids to form dust compositions by grinding, mixing, or wetting the finely divided carrier with a solution of the toxicant and a volatile organic solvent. Similarly, dust compositions containing the aforesaid carbamate derivatives may be compounded from any one or more of the solid surface active dispersing agents previously mentioned, such as bentonite, fullers earth, attapulgite, and other clays. Depending upon the proportions of ingredients, these dust mixtures may be employed either as treating compositions or as concentrates to be subsequently diluted with additional solid surface active dispersing agent or with talc, chalk, gypsum, etc., to obtain the desired amount of toxicant in a composition adapted to be applied to plants, plant growth media, or fungi thereon, for the suppression of plant growth of said fungi. Also, such concentrate dust compositions may be dispersed in water or organic solvent with or without the aid of additional dispersing or emulsifying agent to form spray mixtures.

Dust concentrates, such as above-described, or, alternatively, appropriate crotyl derivative compounds may be intimately mixed with liquid or solid ionic or non-ionic dispersing agents to form spray concentrates. Such concentrates are readily dispersible in liquid carriers to form sprays containing the crotyl derivative in any desired amount.

. -Any of the above crotyl compounds of this invention may also be compounded with suitable water-miscible or'water-immiscible organic liquid and surface active 9 dispersing agents, provided that they do not react with the N-chlorocrotyl compounds, to produce liquid concentrates which may be further formulated with water weather effects. An additional factor to be considered and/or oil to prepare spray mixtures in the forrn'of aqueous dispersions or oil-in-water emulsion composiachieved by administering sufficient N-chlorocrotyl de tions. The exact step to be employed in preparing such rivatives of this invention to eradicate grasses without compositions is within the knowledge of those skilled f t g Oa se eafin the art. Preferred water-immiscible organic liquids Effective control of terrestrial plants in soil may be include petroleum oil and distillates, toluene, xylene, readily achieved by the administration of varies N- cumene and other aromatic hydrocarbon solvents, chlorocrotyl derivatives of this invention. chlorinated aliphatic hydrocarbons, isoparaffin oil and The administration of the present compounds or other alliphatic hydrocarbon solvents. I compositions thereof to plant or plant growth media may be carried out in any manner known to those When the aforesaid crotyl derivatives of this inven- Sklued i art and may be earned out y us.mg dust composltions, sprays or any other modification protion are alkali metal, ammonium, or amine salts, aquevided that an effective dosage 1S supplied. It is to be un- Ous concentrate Composmons readily P l derstood that the total volume orweight of the treating The Salts may be first i l a water'mlsclble composition to be employed is not critical so long as Orgamc Solvent and added to a mlmmal amount of the critical amount of the aforesaid crotyl compound is or they be dlrectly. compounded water or m supplied, which is, in the present instance, about 0.5 to a water-organic sqlvent Usually the use of a 50 pounds per acre. Frequently, the desirability of aprocedure i h Include? addmon a small amount more concentrated or dilute composition depends of a iatepmlsclble orgamc Fi 15 Preferred More' upon a method of application and the area to be covover, in the case of salt compositions, the salt need not ered; hence, the Selection of the concentration and be pre.formed but may be prepariad (hung the total volume or weight may be made by those of ordipoundmg process. Thus dfaslred N'chlomcrotyl nary skill in the art in view of the foregoing teachings. cofnpound and l amlne or morgamf: base may be The present invention is further illustrated in greater mlxed. together m apprpnate amounts m an aqueous detail by the following examples, but it is to be underorgamc Solvent mlxture' stood that the present invention, in its broadest aspects,

is not necessarily limited in terms of the specific tem- The present cofnlfosmon also other peratures, residence times, reactants, pressures, solplant growth modlfymg agents elther as adjullams vents, analytical techniques, separation techniques, supplmemafy .matenals for both terrestrial n and other process conditions by which the compounds aquanc apphcatlons' and compositions described and claimed in this invenln carrying out the methods of the present invention, tion are prepared and used. as they pertain to the growth control of fungi or of plant growth or vegetation, the crotyl derivatives of this 111- EXAMPLE 1 vention are administered to foliage, plant parts, or growth media of the plant species whose pesticide con- 40 trol is desired. The exact amount to be administered va- The Addition of NN Dichloro Methyl Carbamate to ries with the particular type of growth control to be d ugate ienes achieved. It further varies with method of application, i.e., whether the application is to be made to foliage, food, flower, or particular plant part, or to soil or other. NiNdlchloro P carbamate '9 added growth media, and the overall site of application: a droPwlse to a surfed mtrqgoen purged 9 of sheltered area, such as a greenhouse; or an exposed equlmolar amount of coniugated dene methylene area Such as fields; Thus, as f example, in the chloride solution cooled to between -10 and -20C by treatment of grass and weeds, soil application is pre- 3 y ice'isopropanol bathi Fate of addition of the ferred to foliage application and the amounts are govcarpamflte was Such thatothe mtemal temperatllre was erned thereby. Also, weeds present in sheltered areas malmalned bfiween 20 and After addltlon was are o responsive to treatment d i i l dosages complete the reaction mixture was allowed to warm to are usually adequate whereas field applications often room temperature. The solvent was removed at aspiratimes require higher dosages to counteract adverse tor pressure at ambient temperature to yield the crude TABLE I is the plant species to be treated, as well as the presence or absence of desirable plants together with the undesirable species. Thus, selective grass control may be PREPARATION OF N-CHLORO-N-(4-CHLOROCROTYL) METHYL CARBAMATES I Adduct lsomers, C% H% N% R ,R ,R ,R ,R ,R7 Yield b.p.C.(mm) m, by 1,2 nmr, 1,4 Calcd. Found Calcd. Found Calcd Found H, H, H, H, H, 'H, 91 526(0.005) 1.4930 14 86 36.38 36.27 4.58 4.73 7.07 6.98 H, H, CH H, H, H, 82 72-4(0.065) 1.4964 39.64 39.55 5.23 5.35 6.60 6.63 H, H, CH CH H, H 80 83 (0.006) 1.4996 42.49 42.41 5.80 5.99 6.19 6.12 H, H, Cl, H, H, H 82 78 (0.003) l.5095 100 30.99 31.06 3.47 3.90 6.02 6.05 H, H, H, H, H, CH 84 65 (0.01) 1.4852 27 73" 39.64 39.28 5.23 5.32 6.60

""15% 4 ,l-addition product as an oil. The product was then purified by vacuum distillation.

The results obtained using this procedure or its converse, i.e., adding the conjugated diene to a solution of the N,N-dichloro methyl carbamate in methylene chloride solution, are summarized in Table I.

EXAMPLE 2 The Addition of N,N-Dichloro Methyl Carbamate to 1 ,3-Butadiene 1,3-Butadiene (54 g, 1.0 mole) was diluted with nitrogen and slowly passed with stirring into 140 g (0.98 mole) of N,N-dichloro methyl carbamate cooled to 1 C. by a dry ice-acetone bath. The rate of addition was such that the internal temperature was maintained between and C. After addition was complete the reaction was warmed slowly to room temperature. The yield of product was 192 g. A gc analysis indicated a purity of 98% and a 90:10 ratio of 1,4- to 1.2-adducts.

EXAMPLE 3 The addition of N,N-Dichloro Methyl Carbamate to 1,3-Butadiene EXAMPLE 4 The addition of N,N-Dichloro lsopropyl Carbamate to Butadiene-l ,3

1,3-Butadiene (10.6 g, 0.2 mole) was diluted with nitrogen and passed into 34.0 g (0.2 mole) of N,N- dichloroisopropyl carbamate cooled to 10C. by a dry ice-acetone bath. The rate of addition of diene was adjusted so as to'maintain the internal temperature between 5 and 10C. After addition was complete the reaction was warmed slowly to room temperature. The

product weighed 43.2 g. A gc analysis showed an 89:1 1 ratio of 1,4 to 1,2-adducts and a purity of 98%. The product was purified by vacuum distillation to give an 85% yield of adduct, b.p. 757C. (0.006 mm), n 1.4762.

, Calcd. for c H, c1,No ;c, 42.49; H, 5.80; N, 6.20. Found: C, 42.53; H, 5.85; N, 6.32.

' EXAMPLE 5 The Addition of N,N-Dichloro lsopropyl Carbamate to lsoprene lsoprene (10.2 g, 0.15 mole) was added dropwise with stirring to a nitrogen purged solution of 25.8 g.

(0.15 mole) of N,N-dichloro isopropyl carbamate in 25 ml of methylene chloride solution cooled to -l0C. The rate of addition was such that the internal temperature was maintained between 0 and 5C. After addition was completed, the reaction was slowly warmed to room temperature. The solvent was evaporated to give 36 g. of crude product. Distillation gave a 94% yield of mono adduct b.p. 7C (0.007 mm), m, 1,4814. An examination of the nmr spectrum of this mono adduct indicated that the material consisted of an 85:15 mixture of 1,4- and 4,1-adducts.

Calcd. for C H, Cl NO C, 52.55; H, 7.84; N, 6.81. Found: C, 55.32; H, 8.16; N, 6.81.

EXAMPLE 6 The Addition of N,N-Dichloro lsopropyl Carbamate to 2,3-Dimethyl-1,3-Butadiene.

' The reaction 0.08 mole of N,N-dichloro isopropyl carbamate with 0.08 mole of 2,3-dimethyl-l,3- butadiene using the above procedure gave 15.4 g (0.065 mole, 82%) of N-chloro-N-Z,3-dimethyl-4- chlorobut2-ene-( l isopropyl carbamate b.p. 813C. (0.005 mm), m, 1.4850.

Calcd. for C H C1 NO C. 47.25; H, 6.75; N, 5.51. Found: C, 47.30; H, 7.06; N, 5.30.

EXAMPLE 7 The Addition of N,N,N, N-Tetrachloro Ethylene Glycol Bis Carbamate to Chloroprene A solution of 9.8 g (0.034 mole) of N,N,N, N'- tetrachloro ethylene glycol bis carbamate in 15 ml of methylene chloride solution was added dropwise with stirring to a solution of 6.1 g (0.068 mole) of freshly distilled chloroprene in 15 ml of methylene chloride cooled to 20C. in a dry ice-acetone bath. The rate of addition was such that the internal temperature remained below 10C. After addition was complete the reaction was warmed slowly to room temperature and the solvent evaporated to yield 15.8 g of oily adduct. The material was homogeneous on tlc. The nmr indicated exclusive 1,4-addition with a small amount of methylene chloride as the chief contaminant. A sample was stored under high vacuum at room temperaturefor 15 hours and then submitted for elemental analysis.

Calcd. for C H Cl NO C, 31.12; H, 3.05; N, 6.05 Found: C, 30.74; H, 3.25; N, 6.08.

EXAMPLE 8 The Addition of N,N,N, N-Tetrachloro Ethylene Glycol Bis Carbamate to 1,3-Butadiene The reaction was performed as described in Example 3 to give 73 g. ofadduct as an oil from 53.6 g. of N,N,N, N'-tetrachloro ethylene glycol bis carbamate. An nmr spectrum of this material indicated that it consisted of an 85:15 mixture of 1,4- and 1,2-adducts.

Calcd. for C H Cl NO N, 7.11 Found: N, 7.14

EXAMPLE 9 General Procedure for the Reduction of N-Chloro-N- [4-chlorocrotyl-( 1 Carbamates.

13 A solution of N-chloro:N-[4-chlorocrotyl-,(1)] carbamate in methylene chloride'was vigorously stirred at ambient temperature with an aqueous solution of a three-fold excess of sodium sulfite until the organic layer failed to give a positive potassium iodide test. The layers were separated and the methylene chloride phase was washed with water and dried over anhydrous potassium carbonate. The methylene chloride was evaporated at ambient temperature to yield the reduced product as a liquid or solid which was then purified by the appropriate method. The results are listed in Table II.

TABLE II v 14 EXAMPLE 11 The Addition of N,N-Dichloro Methanesillfonamide to Chloroprene A solution of 30.0 g (0.183 mole) of N,N-dichloro methanesulfonamide in 75 ml of methylene chloride was added dropwise to a stirred solution of 16.2 g (0.183 mole) of chloroprene in 50 ml of methylene chloride and cooled to 20C. in a dry. ice-isopropanol bath. The rate of addition was controlled so that the internal temperature of the reaction mixture remained between l and 0C. After addition was complete the reaction mixture was allowed to slowly come to room temperature. The solvent was removed at aspira- Reduction of N-Chloro-N-Crotyl Carbamates with Sodium Sulfite l tor pressure to i ld 46 g f lid R lli a i o O from carbon tetrachloride gave 41.1 g (89%) of 1,4- adduct m.p. 702C. I R|OCN-R2 Na SO R oCNHR l 0 EXAMPLE 12 I Addition of N,N-Dichloro sulfonamides To R|OCNHR2 R. R2 Yield mp) Q Con ugated Dienes n General N,N-dichlorobenzene sulfonamide,-4-chlorobenzene CH3 CH2 CH=CH CH2G 89 sulfonamide, and methane sulfonamide were reacted with butadiene and chloroprene in a manner described 5 I in Example 5. CHa 76 Pertinent data regardng the preparation of the result- Cl mg N-chloro-N-crotyl sulfonamides are given in Table III CH CH -C=CH-CH CI 78 58-9 v C H3C H= TABLE III CH3 CHz-C C CH2CVI 84 PREPARATION OF N-CHLORO-N-CROTYL SULFONAMIDES CHCH=CHCH CI i R"SO NCl -l-CH ==CCH=CH R"SO NCH C=C l-lCH Cl CH3 (84-6C/ I cu CH 'CH=C HCHCl s2 0004mm) j X Cl X R" x 7Y'ld' 5 CH3 40 0 le mpC c u H i c,u, CH CH=CHCl -l Cl 78 61-2 Z C1 33 pCl-CJ-l. 7H 85 1 26-7 3 pClC 'H, (:1 I '85 87-8 I ca it 85 52-3 l C3H1 CH2C=CHCH2CI 8| 5 l2 CH3 Cl 89 702 EXAMPLE l0 Satisfactory elemental analyses were obtained on all adducts.

The Addition of N,N-Dichloro Benzenesulfonamide to 1,3-Butadiene 1,3-Butadiene (1.6g, 0.03 mole) was diluted with nitrogen and slowly distilled into a stirred solution of N,N-dichloro benzenesulfonamide (5.9 g, 0.026 mole) in 15 ml of methylene chloride cooled to 10C. by a dry ice-isopropanol bath. The rate of addition was such EXAMPLE 13 General Procedure for the Reduction of N,N-Dichloro sulfonamide-Conjugated Diene Adducts A solution of adduct in methylene chloride was vigorously stirred at room temperature with an aqueous solution containing a threefold excess of sodium sulfite until the organic layer failed to give a positive potassium iodide test. The organic layer was separated, dried over sodium sulfate, filtered and evaporated to give the reduced product which was then purified by recrystallization. Pertinent data regarding the reduction of N- chloro-N-crotyl sulfonamides are given in Table IV.

Satisfactory elemental analyses were obtained on all reduction products.

EXAMPLE 14 Addition of N,N-Dichloro-N, N-Dimethylsulfamide to Chloroprene A solution of 12.2 g (0.063 mole) of N,N-dichloro- N, N'-dimethylsulfamide in 50 ml of methylene chloride was added dropwise to a stirred solution of 5.6 g (0.063 mole) of freshly distilled chloroprene in 25 ml of methylene chloride cooled to 15C. by a dry ice isopropanol bath. The rate of addition was regulated so that the internal temperature remained between 10 SOIL FUNGICIDAL ACTIVITY OF CARBAMATES AND REDUCED and 5C. After addition was complete the reaction was warmed slowly to room temperature and the solvent evaporated to yield an oil. The oil was dissolved incarbon tetrachloride and pentane was added to the cloud point. Upon cooling 15.0 g, 84%, of 1,4-adduct m.p. 368C. crystallized. An analytical sample had a m.p. 38-40C.

Anal. Calcd. for C H CI N O S: C, 25.59; H,3.94; N, 9.95; S,11.39. Found: C, 25.64; H, 3.91; N, 10.65;8, 11.46.

EXAMPLE 15 Use of N-Chloro-N-Crotyl Carbamates and Their Reduction Products as Soil Fungicides Using standard techniques both the N,N-dichloro methyl carbamate-1,3-butadiene adduct and its reduced derivative were screened by the Wisconsin Alumni Research Foundation as soil fungicides. The

test organism used for cucumbers was Pythium sp., for cotton, Rhizoctonia solani and for tomatoes, F usarium oxysporum. The data obtained are listed in Table IV. The data showed that both the adduct and its reduced derivative show a fungicidal effect. For example, in the case of the N,N-dichloro methyl carbamate adduct treated soil eight of the cotton plants survived even though they were inoculated with Pythium sp. In

contrast, in the untreated but inoculated soil, none of the cotton plants survived.

TABLE V N- CHLORO-N-CROTYL DERIVATIVES **Number of 'Plants Survfiy.

' 7 Reference Structure Conc. Soil Cotton Cucumber Tomato ii Table I CH OCN-CH CH=CH-CH Cl 0-5 Inoc.* 8 9 11 I 0.5 Uninoc.* 9 l0 16 Table II CH OCNHCH CH=CHCH C1 0.5 Inoc' 9 1O 6 p Uninoc. 9 1O 2O 9 Table III CH OCNHCH C=CHCH Cl O. l Inoc. O 6 17 Uninoc. 7 18 Untreated Inoc. O O 6 Uninoc. 8 9 16 Inoculated Uninoculated Each flat both inoculated and" uninoculated was seeded with cotton, 10 cucumber and 20 t'omatoe seeds.

EXAMPLE 16 Use of N-Chloro-N-Crotyl Carbamates and Their Reduction Products on Herbicides Samples of unknown activity are tested at a concentration equivalent to 20 lbs. per acre. Atrazine and 2,4-D are used as positive standards.

Pre-emergence tests Duplicate paper pots filled with a soil mixture are seeded with snap beans, cotton, corn, wheat, mustard, pigweed, crabgrass and foxtail. Immediately after seeding the soil is sprayed with the sample solution. Growth occurs under artificial light with overhead irrigation. The plants are observed for about IO days and an injury rating is given in comparison with untreated controls.

Post-emergence tests Duplicate paper pots filled with vermiculite are seeded with the same plants employed in the pre-emergenee tests. Growth occurs under artificial light with irrigation provided by placing the porous pots in a small amount of water in stainless steel trays. After about ten days when the test plants reach a suitable size they are sprayed with the sample. 25

Observations are made for ten days and an injury rating is given in comparison with untreated controls.

The results are shown in Table VI. The data show that although the N-chlorocrotyl carbamates of the 18 EXAMPLE 17 Use of N-Chloro-N-Crotyl Sulfonamides as Soil Fungicides The N,N-dichlor0 methyl sulfonamide-chloroprene adduct was screened by the Boyce Thompson Institute for Plant Research, Inc. as a soil fungicide. The following procedure was used.

The mycelial growths on Pythium, Fusarium and Rhizoctonia were rated 5, 4, 3 indicating from complete to substantial control.

It will be understood that the foregoing description is merely illustrative of preferred embodiments and speciftc examples of the present invention and that varia- 30 tions may be made in such embodiments and examples TABLE VI POS'IJLMERGENCIZ HERBICIDAI. 'I'ES'I DATA FOR NCHLORQN-CROTYL CARBAMATES AND THEIR REDUCTION PRODUCTS Rele rcncc Conc. Mustard Pigweed C rah-Grass Foxtail C orn Wheat Cotton Beans Table Structure 70"" Post* Post* Post" Post Post* Post Post" ost* l (H;,()(N((l )(H. .(H=CHCH ,CI ()5 5G 5G 5T 3T 4T 3T 40 46 n 4W 5W 5W 2U ll (H OtNHcH CH fHCH Cl 0.5 5G 5G 4T 3T 5T 3T 4G 36 u 4W 5W 2W lL 3W IL 3U l (H=(H(H 0.5 40 5G 3T 3T 2L 2L 3L 2L 4W 4W 2L 21. 2T 2T IS 26 O l (H ()(N((l)('H (((H;,)=(('H;. 0.5 4G 5G 3T 4T 4T 2L 2I..IS 3L .I 4N SW 21. Zl 3W 2T 30 2G CH CI ll (H;.()(NH('H,C(CH ('HCH fl 0.5 20 4G 2T II .T 2L ll. 31. n l I. 4W 2L 2L ll. 2T IS 26 Untreated 0 (l (l l) 0 t) t) I) 0 Legend Degree of Injury Type of Injury 0 none 3 moderately severe C (lilorosis NG No Growth TB Terminal Bud I slight 4 severe [i lipinasty R Reduction U Leaf Curl Upward Z Moderate 5 death M Mottled Nl-' Nodulc Formation ""05"; concentration cmrcsponds lo a rate ol' appros 7 lbs acre. Prior to tcsling. no Degree of lnjl|r was present in l'iinergcnts.

G General Necrosis H Hypertrophy L Local Necrosis R(i Reduced Germination W wilting S Stunting SS Stem Swelling SC Stem Curling T Tip hurn present invention are not active as pre-emergence herbicides, they are highly active as post-emergence herbicides when used at a concentration of 0.5% which is equivalent to 20 lbs. per acre.

by those skilled in the art without departing from the 5 spirit and purview thereof.

What is claimed is: l. A selective monoaddition process for the preparation of C to C alkyl N-chloro-N-(4-chlorocrotyl-l) carbamate compounds, comprising reacting a C, to C N,N-dichloro alkyl carbamate compound with a C to C conjugated diene at a temperature of between about 80 and about 100C. and pressures about 1 and about atmospheres in the liquid phase in the absence of added catalyst.

2. A process for the preparation of C to C alkyl N-chloro-N-(4-chlorocrotyl-l) carbamate compounds comprising reacting a C to C alkyl N,N-dichloro carbamate with a C to C conjugated diene at a temperature of between about 80 and about 100C. and pressures of between about I and about 10 atmospheres in the liquid phase.

3. A process according to claim 2 wherein said carbamate is selected from the group consisting of C to C alkyl carbamates and C to C alkylene bis carbamates.

4. A process according to claim 1 wherein said conjugated diene is selected from the group consisting of isoprene, chloroprene, 1,3-butadiene, piperylene, 2,3- dimethyl butadiene, 2,3-dichlorol ,3-butadiene, 2,4-dimethyl-l,3-pentadiene, Z-ethyl-l, 3-butadiene, 1,3-hexadiene, 2,4-hexadiene, Z-methyl-l ,3- pentadiene, and 4-methyl-l,3-pentadiene.

5. A process according to claim 1 wherein the reaction step is conducted in the presence of a suitable solvent.

6. A selective monoaddition process for the preparation of C, to C N-chloro-N-(4-chlorocrotyl-1) car- 30 bamate compounds comprising reacting an N,N- dichloro carbamate compound having the formula R OCNClg wherein R is a C, to C alkyl, a C to C alkyl substi- 4O tuted with halo, with a C to C conjugated diene of the formula ature of between about 80 and about 100C. and pressures about 1 and about 10 atmospheres in the liquid phase using a l to l to l to 5 mole ratio of the above reactants in the absence of added catalysts.

7. A selective monoaddition process for the preparation of N-chloro-N-(4-chlorocrotyl-l carbamate compounds comprising reacting an N,N-dichloro carbamate compound of the formula R OCNCl wherein R, is a C to C alkyl with a conjugated diene of the formula R R R5 C C C C I I R3 R7 wherein R to R are hydrogen, chlorine. fluorine, methyl at a temperature of between about and about C. and pressures about 1 and about 5 atmospheres using a 1:1 to 1:5 ratio of the above reactants in the absence of added catalysts.

8. A selective monoaddition process according to claim 7 wherein R is methyl and R to R are hydrogen.

9. A selective monoaddition-reduction process for the preparation of N-(4-chlorocrotyl-l) carbamate compounds comprising adding an N,N-dichloro carbamate compound of the formula R ooncl wherein R is a C to C alkyl radical, to a conjugated diene of the formula c c c c wherein R to R are hydrogen, chlorine, fluorine, methyl at a temperature of between about 80 and about 100C. in the absence of added catalyst and pressures about 1 and about 10 atmospheres in the liquid phase to obtain a major amount of a monoadduct of the formula R OCN C C C C Cl I I I Cl R3 R and reducing the N-chloro group of said monoadduct with sodium sulfite at a temperature of -20 to 100C.

10. A selective monoaddition-reduction process according to claim 9 wherein R is methyl, R to R are hydrogen.

ll. Compounds having the formula l y C C C c c1 wherein R, is C, to C alkyl, R, to R are hydrogen, chlorine, fluorine, C, to C alkyl.

12. Compounds according to claim 11 wherein R, is methyl, ethyl, propyl and R to R are hydrogen, chlorine, fluorine, methyl.

13. Compounds having the formula R R R R 9 l I I I R,ocN-c-c=c-c-c1 wherein R, is one selected from the group consisting of C, to C alkyl, a C, to C alkyl substituted with halo, 1

R to R are monovalent radicals selected from the group consisting of hydrogen, chlorine, fluorine, C, to C alkyl, C, to C alkyl substituted with halo, and X is selected from the group consisting of chlorine and hydrogen.

l4. Compounds having the formula R OCIY CH2 CH CHCH Cl wherein R, is an aliphatic radical having from 1 to 30 carbon atoms and selected from the group consisting of unsubstituted alkyl and halo, substituted alkyl radicals; and X is selected from the group consisting of hydrogen and chlorine.

15. Compounds having the formula R1OCN CH CCl CHCH Cl.

wherein R, is an aliphatic radical having from 1 to 30 carbon atoms and selected from the group consisting of unsubstituted alkyl and halo, substituted alkyl radicals; and X is selected from the group consisting of hydrogen and chlorine.

l6. Compounds having the formula R1OCI\I CH2 e CH CH Cl X CH wherein R, is an aliphatic radical having from 1 to 30 carbon atoms and selected from the group consisting of unsubstituted alkyl and halo, substituted alkyl radicals; and X is selected from the group consisting of hydrogen and chlorine.

l7. Compounds having the formula u R OC N ca c c CH Cl OC N CH CH CHCH Cl wherein R, is an aliphatic radical having from 1 to 30 carbon atoms and selected from the group consisting of unsubstituted alkyl and halo, substituted alkyl radicals; and X is selected from the group consisting of hydrogen and chlorine.

l9. Compounds having the formula wherein R, is an aliphatic radical having from 1 to 30 carbon atoms and selected from the group consisting of unsubstituted alkyl and halo, substituted alkyl radicals;

and X is selected from the group consisting of hydrogen and chlorine.

20. N-[4-chlorocrotyl-(1)] methyl carbamate and the N-chloro derivative thereof.

21. N-[4-chlorocrotyl-(l)]isopropyl carbamate and the N-chloro derivative thereof.

22. N-[2-methyl-4-chlorobut Z-ene- (1)]methylcarbamate and the N-chloro derivative thereof.

23. N-[2-methyl-4-chlorobut-2-ene-( 1)] isopropylcarbamate and the N-chloro derivative thereof.

24. N-[ 2,3-dimethyl-4-chlorobut-2-ene-(1)] methyl carbamate and the N-chloro derivative thereof.

25. N-[2,3-dimethyl-4-chlorobut-2-ene-(1)] isopropyl carbamate and the N-chloro derivative thereof.

26. N-[2,4-dichlorobut-2-ene-(1)] methyl carbamate and the N-chloro derivative thereof.

27. A compound of the formula CH OCN-CH2 CH=CH CH-C l Cl CH 

1. A SELECTIVE MONOADDITION PROCESS FOR THE PREPARATION OF C1 TO 130 ALKYL N-CHLORO-N-(4-CHLOROCROTHYL-1) CARAMATE COMPOUNDS, COMPRISING REACTING A C1 TO C30 N,N-DICHLORO ALKYL CARBAMATE COMPOUND WITH A C4 TO C30 CONJUGATED DIENE AT A TEMPERATURE OF BETWEEN ABOUT-80* AND ABOUT 100*C. AND PRESSURES ABOUT 1 AND ABOUT 10 ATMOSPHERES IN THE LIQUID PHASE IN THE ABSENCE OF ADDED CATALYST.
 2. A process for the preparation of C1 to C30 alkyl N-chloro-N-(4-chlorocrotyl-1) carbamate compounds comprising reacting a C1 to C30 alkyl N,N-dichloro carbamate with a C4 to C30 conjugated diene at a temperature of between about -80* and about 100*C. and pressures of between about 1 and about 10 atmospheres in the liquid phase.
 3. A process according to claim 2 wherein said carbamate is selected from the group consisting of C1 to C30 alkyl carbamates and C1 to C12 alkylene bis carbamates.
 4. A process according to claim 1 wherein said conjugated diene is selected from the group consisting of isoprene, chloroprene, 1,3-butadiene, piperylene, 2,3-dimethyl butadiene, 2,3-dichloro-1,3-butadiene, 2,4-dimethyl-1,3-pentadiene, 2-ethyl-1, 3-butadiene, 1,3-hexadiene, 2,4-hexadiene, 2-methyl-1,3-pentadiene, and 4-methyl-1,3-pentadiene.
 5. A process according to claim 1 wherein the reaction step is conducted in the presence of a suitable solvent.
 6. A selective monoaddition process for the preparation of C1 to C30 N-chloro-N-(4-chlorocrotyl-1) carbamate compounds comprising reacting an N,N-dichloro carbamate compound having the formula
 7. A selective monoaddition process for the preparation of N-chloro-N-(4-chlorocrotyl-1) carbamate compounds comprising reacting an N,N-dichloro carbamate compound of the formula
 8. A selective monoaddition process according to claim 7 wherein R1 is methyl and R2 to R7 are hydrogen.
 9. A selective monoaddition-reduction process for the preparation of N-(4-chlorocrotyl-1) carbamate compounds comprising adding an N,N-dichloro carbamate compound of the formula
 10. A selective monoaddition-reduction process according to claim 9 wherein R1 is methyl, R2 to R7 are hydrogen.
 11. Compounds having the formula
 12. COMPOUNDS ACCORDING TO CLAIM 11 WHEREIN R1 IS METHYL, ETHYL, PROPYL AND R2 TO R7 ARE HYDROGEN, CHLORINE, FLUORINE, METHYL.
 13. Compounds having the formula
 14. Compounds having the formula
 15. Compounds having the formula
 16. Compounds having the formula
 17. Compounds having the formula
 18. Compounds having the formula
 19. Compounds having the formula
 20. N-(4-chlorocrotyl-(1)) methyl carbamatE and the N-chloro derivative thereof.
 21. N-(4-chlorocrotyl-(1))isopropyl carbamate and the N-chloro derivative thereof.
 22. N-(2-methyl-4-chlorobut-2-ene-(1))methylcarbamate and the N-chloro derivative thereof.
 23. N-(2-methyl-4-chlorobut-2-ene-(1)) isopropylcarbamate and the N-chloro derivative thereof.
 24. N-(2,3-dimethyl-4-chlorobut-2-ene-(1)) methyl carbamate and the N-chloro derivative thereof.
 25. N-(2,3-dimethyl-4-chlorobut-2-ene-(1)) isopropyl carbamate and the N-chloro derivative thereof.
 26. N-(2,4-dichlorobut-2-ene-(1)) methyl carbamate and the N-chloro derivative thereof.
 27. A compound of the formula 